Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
  • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
  • C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
  • C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring

Definitions

• the present invention relates to a fluorine-substituted benzoate and a method for producing the same.
• the present invention relates to a novel substituted benzoic acid derivative
• one of and Ar ′ is a ⁇ - or 0-fluorophenyl group, and the other is an m-fluorophenyl group, and a phenyl-substituted phenyl benzoate represented by the formula: .
• the fluorine-substituted phenyl benzoate represented by the general formula (I) can be used as a raw material for producing a fluorophenol which is useful as a synthetic intermediate for pharmaceuticals, agricultural chemicals or functional materials. That is, the compound represented by the general formula (I) can be easily derived into fluorophenol by subjecting it to a hydrolysis treatment.
• methods for SS of fluorophenol include: (a) a method of subjecting fluoroaline to a Sandmeyer reaction [Ger. Offen 2,426,994 (19975)]; and (b) a Seaman reaction of aminophenol. CDunker, MFW; Star key, ⁇ . ⁇ ., J. Am. Chem. Soc., 1939, 11, 2003, Finger and GC; Oester 1 ing, RE, J. Am. Chem. Soc., 1956, 78.2593]; (c) bromo A method for decomposing fluorobenzene by force [ ⁇ ] [Boudakian, MM; Eber RJ; Mcarthur, RE. J. Org. Chem., 1961, 26,
• the method (a) has a problem in availability of raw materials and requires the use of a large amount of an acid such as sulfuric acid. Barbara.
• the method (b) requires non-reusable high-purity hydrofluoric acid.
• the method (c) not only the reaction conditions are severe, but also the defluorination reaction is liable to occur simultaneously, and tends to produce unsubstituted phenol which is difficult to separate from fluorophenol.
• the method (d) it is not easy to obtain raw materials other than p-fluoroanisole, and therefore, it is limited to only the method for synthesizing the P-isomer of fluorophenol.
• the present inventors have conducted intensive studies on the production method of fluorophenol industrially.As a result, this time, the present inventors have found that a fluorine-substituted phenyl benzoate represented by the above-mentioned general formula (I), which is useful as a precursor thereof, c are those that led to the completion of the industrially advantageous manufacturing method
• the fluorine-substituted benzoic acid benzoate represented by the general formula (I) provided by the present invention is represented by the general formula:
• A is a fluorophenyl group
• Fluoro-benzoic acid represented by the formula ( ⁇ ) is a compound known per se], for example, by oxidation of fluorotoluene, etc.] j Inexpensive and easily available Is a compound that can be
• the oxidative decarboxylation reaction of the fluorobenzoic acid represented by the above general formula (H) is usually carried out in a solvent-free state or preferably at a relatively high boiling point (preferably 180 ° C) which can be refluxed at the reaction temperature.
• a relatively high boiling point preferably 180 ° C
• an oxidizing agent in an insoluble organic solvent such as getyl fumarate, diphenyl ether, tetraglyme, decalin, etc.
• the oxidizing agent usable for ft for example, copper ( ⁇ ) salt, oxygen and a catalytic amount of copper, copper (I) salt or copper (H) salt, or a combination of copper oxide and the like can be used.
• Copper or copper salts that can be used include, for example, copper powder, porous copper; copper halide (1), copper (I) halide; copper fluorobenzoate, copper acetate and other organic acid salts of copper; Examples thereof include copper carbonate and copper hydroxide.
• the copper ( ⁇ ) salt is used in an amount approximately equal to the amount of the fluorobenzoic acid represented by the general formula (H) in a preferable amount. Preferably, it is used in a molar amount of 0.5 to 2 times. If necessary, a co-catalyst such as magnesium oxide, zirconium oxide or manganese dioxide may be used.
• the above reaction is generally carried out at a temperature of about 180 ° C or higher, but from the viewpoint of the reaction rate, reaction efficiency such as prevention of side reactions, etc., at a temperature within the range of 200 to 260 ° C. It is preferred to do so.
• the compound represented by the above general formula) produced by the above reaction is separated from the reaction mixture by various means known per se, for example, chromatography, crystallization, recrystallization, distillation, extraction, etc., and / or It can be purified.
• the fluorobenzoic acid of the formula ( ⁇ ) reacts with the oxidizing agent to form copper fluorobenzoate ( ⁇ ) as an intermediate, which is produced under the above temperature conditions. It is presumed that the compound is converted into the desired fluorinated phenyl benzoate of the formula (I). This is supported by the experiments shown in Reference Examples 1 and 2 described below. In this reference example, full-year-old copper benzoate ( ⁇ ) is exposed to the above-mentioned temperature conditions. It has been confirmed that fluorinated benzoic acid phenyl is formed.
• the fluorinated phenyl benzoate represented by the general formula (I) provided by the present invention j is hydrolyzed.
• the production of the phenyl benzoate and its hydrolysis can be performed in a "one pot", in which case, as described in Examples 6 and 7 below,
• a copper catalyst and possibly a co-catalyst to the fluorobenzoic acid represented by the general formula ( ⁇ ) and supplying oxygen and superheated steam]
• a 1-volume Claisen flask for distillation was inserted into a 1-volume distillation flask, and P-fluoro mouth benzoic acid (1.4 ⁇ ), powdered porous copper (0.159), and getyl fumarate (0.3 ⁇ ) as a solvent were added.
• the mixture was heated to 240 C on an oil bath, and oxygen was blown through the oxygen introducing tube at a rate of 30 min from the bottom of the reaction solution for 50 minutes. Due to unreacted oxygen and reaction! )
• the generated carbon dioxide was released out of the system through the branch pipe of the Claisen flask for distillation. After cooling, the reaction mixture was washed out using a ether and separated into an excess residue and a liquid.
• M-Fluorobenzoic acid 49 ⁇ , powdered porous copper 0.223 ⁇ , and getyl fumarate 0.5 ⁇ as a solvent were added to a 30-volume Claisen flask for distillation into which an oxygen inlet tube was inserted. And heat to 250 ° C to allow oxygen to pass through the oxygen inlet tube to the bottom of the reaction solution] at a speed of 40 Zmin for 60 minutes. I blew it. After cooling, m-fluorobenzoic acid 0.602 ⁇ was recovered from the iF excess residue by the same operation as in Example 1. '/ From the door liquor, column chromatography!
• M-Fluorobenzoic acid p-Fluorophenyl 0.406 ⁇ and m-Fluoro'-benzobenzoic acid 3.81 were obtained.
• the yield of m-fluorobenzoic acid p-fluorophenol was 5.0% and the selectivity was 50.2 0.2.
• Example O-Fluorobenzoic acid 4.9 ⁇ , powdered porous copper 0.223 ⁇ , and getyl fumarate 0.5 ⁇ as a solvent were added to a 30-volume Claisen flask for distillation with an oxygen inlet tube, and 240 TC in an oil bath. , And oxygen was blown through the oxygen inlet tube at a rate of 40 min from the bottom of the reaction solution for 60 minutes. After cooling, the same operation as in Example 1 was carried out.] 9, 1.014 ⁇ of o-fluorobenzoic acid was recovered from the excess residue.
• P-Fluorobenzoic acid 1.4 ⁇ , cupric hydroxide 0.976 ⁇ , and tetraglyme 3 as a solvent were added to a 25 ⁇ volume eggplant-shaped flask equipped with an air cooling tube, and stirred with a magnetic stirrer. On the oil bath
• the mixture was heated to 240 ⁇ and sewed for 60 minutes. After cooling, the reaction mixture was washed with ether, and after passing through celite, the solution was concentrated and subjected to column chromatography.
• the m-fluorophenol produced by the reaction] 9 was subjected to steam distillation, passed through a distillation branch pipe, cooled, and collected as a distillate.
• the unreacted oxygen and the reaction] were released through the distillation branch pipe to the outside of the system.
• the gas was introduced.]
• the argon gas was being blown in, the internal temperature was lowered to 120 ° C, water was added, and the remaining m-fluorophenol in the reactor was expelled together with the water.
• the organic matter in the distillate is extracted with ether.]
• the fluorine-substituted phenyl benzoate represented by the general formula (I) is provided as a raw material for producing fluorophenol useful as an intermediate for synthesizing pharmaceuticals, agricultural chemicals or functional materials.

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• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1984
  • 1984-10-08 JP JP59209895A patent/JPS6187646A/ja active Granted
• 1985
  • 1985-10-08 DE DE8585904884T patent/DE3579916D1/de not_active Expired - Lifetime
  • 1985-10-08 EP EP85904884A patent/EP0203195B1/en not_active Expired - Lifetime
  • 1985-10-08 WO PCT/JP1985/000556 patent/WO1986002067A1/ja not_active Ceased
  • 1985-10-08 US US06/878,862 patent/US4705884A/en not_active Expired - Fee Related

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